JP2000119307A - Polymerization initiator system and production of polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization initiation system useful for producing a polymer having a narrow molecular-weight distribution and a controlled molecular weight. SOLUTION: A vinyl-based monomer is radically polymerized in a living way in the presence of a polymerization initiator system composed of a metal complex (A) of the formula (A is carbon or phosphorus atom; M is a transition metal element; X is an organic group which may contain an oxygen atom or a nitrogen atom; (k) is an integer of 2-8; (m) is 1 or 2) and a radical initiator (B). In the metal complex (A), the metal element M is a transition metal element of the groups 7-11 of the periodic table. The radical initiator (B) is an azo compound, an organic peroxide, an inorganic peroxide, or the like. The ratio of the metal complex (A) and the radical initiator (B) is the former/the latter of about 0.1/1 to 10/1 (molar ratio).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerization initiator system comprising a specific metal complex and a radical initiator, a polymer obtained by using the polymerization initiator system, and a method for producing the polymer.

[0002]

2. Description of the Related Art Physicochemical properties of polymers (mechanical strength,
Fluidity, heat resistance, compatibility with other resins, etc.) are greatly affected by the primary structure of the polymer (eg, molecular weight, molecular weight distribution, copolymer structure, terminal group structure, etc.). Therefore, in order to obtain a polymer having desired properties, it is effective to control the primary structure. As a method for controlling the primary structure, living polymerization or the like is performed. The living polymerization can control the terminal structure, can perform block copolymerization, and is useful for obtaining a polymer having a narrow molecular weight distribution. Usually, ionic polymerization (anionic polymerization, cationic polymerization, etc., particularly anionic polymerization) is used. It's being used. However, the polymerization system is easily affected by impurities (water, oxygen, etc.), solvents, and the like, and requires high-purity monomers, polymerization in an inert atmosphere and at a low temperature. In addition, it is economically disadvantageous and industrialization is difficult.

On the other hand, as a polymerization method which is hardly affected by impurities and solvents, there is radical polymerization. Since radical polymerization is not easily affected by these impurities, the operation is simple, and it can be applied to various monomers, and various polymerization methods (bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc.) can be used. It is widely used at the laboratory level and also industrially. However, in the radical polymerization, since a chain transfer reaction and a termination reaction occur, it is difficult to control the terminal structure, and the molecular weight distribution tends to be wide. In addition, it is difficult to produce a block copolymer by an ordinary method.

Recently, even in the case of radical polymerization, a method for controlling a molecular weight to obtain a polymer having a narrow molecular weight distribution, for example,
A method in which radical polymerization proceeds in a living manner (living radical polymerization method) has been found, and it is becoming possible to control the primary structure.

[0005] Makromol. Chem., Rapid Commun., 3, 127
(1982), Otsu et al. Proposed iniferter polymerization. However, in this method, it is difficult to obtain a polymer having a narrow molecular weight distribution.

Macromolecules, 26 , 2987 (1993) and W
O94 / 11412 describes that polystyrene having a narrow molecular weight distribution can be obtained by a method using a stable radical such as 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). . But,
In these methods, coloring occurs depending on conditions, and it is economically disadvantageous.

Macromolecules, 28 , 1721 (1995), JP-A-8-41117, J. Am. Chem. Soc., 117 , 561.
4 (1995), Macromolecules, 28 , 7901 (1995) and WO
No. 96/30421 describes that living radical polymerization of methyl methacrylate and styrene has been achieved by a method using a transition metal complex, and a polymer having a narrow molecular weight distribution can be obtained. However, in these methods, since the initiator and the transition metal complex contain a halogen element, the halogen element is also introduced into the polymer, and the elimination of the halogen element reduces the physical properties of the polymer and generates harmful substances during incineration. Or may be done. Also, J. Am.
Chem. Soc., 117 , 5614 (1995), Macromolecules, 28 ,
In 7901 (1995) and WO96 / 30421, bipyridine is used as a ligand of the metal complex. However, the solubility of the complex is poor, and the solvent used is limited. It is necessary to use a special bipyridine such as nonylbipyridine.

[0008] Macromolecules, 28 , 7572 (1995), Macro
molecules, 30 , 7692 (1997) and Macromolecules, 31 ,,
545 (1998) discloses that a vinyl monomer is polymerized in the presence of AIBN, a metal halide and a ligand. However, in these methods, a halogen element is introduced into the polymer.

JP-A-8-245710 discloses polymerizing a vinyl monomer in the presence of a radical initiator, a trivalent ruthenium compound and a monomer activator such as a Lewis acid. . This document describes that the radical polymerization reaction proceeds in a living manner and the molecular weight and molecular weight distribution of the obtained polymer can be controlled. However, this method also introduces a halogen element into the polymer.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel polymerization initiator system which can proceed in a living manner even in the case of radical polymerization, a polymer obtained by using the same, and a polymer obtained by using the same. It is to provide a manufacturing method.

Another object of the present invention is to provide a polymerization initiator system containing no halogen element and capable of controlling the primary structure such as the molecular weight and molecular weight distribution of the polymer, a polymer obtained using the same, and a method for producing the polymer. Is to provide.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, when a polymerization initiator system is constituted by a specific metal complex and a radical polymerization initiator, a vinyl monomer Can be radically polymerized in a living manner, and the molecular weight and molecular weight distribution of the polymer can be controlled, and the present invention has been completed.

That is, the present invention provides the following formula (1)

[0014]

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Wherein A represents a carbon or phosphorus atom;
Represents a transition metal element, and X represents an organic group which may contain an oxygen atom or a nitrogen atom. k represents an integer of 2 to 8, and m represents 1 or 2. ) Constitutes a polymerization initiator system with the metal complex (A) and the radical initiator (B). In the metal complex (A), the metal element M may be a transition metal element belonging to Groups 7 to 11 of the periodic table. As the radical initiator (B), azo compounds, organic peroxides, inorganic peroxides and the like can be used. Metal complex (A) and radical initiator (B)
Is about 0.1 / 1 to 10/1 (molar ratio).

In the present invention, in the presence of the polymerization initiator system,
A polymer obtained by polymerizing a vinyl monomer or the like and a method for producing the polymer are also included.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polymerization initiator system of the present invention is represented by the following formula (1) and comprises a metal complex (A) having a dithio compound as a ligand and a radical initiator (B). It is useful for living polymerization of a vinyl monomer.

[0018]

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Wherein A represents a carbon or phosphorus atom;
Represents a transition metal element, and X represents an organic group which may contain an oxygen atom or a nitrogen atom. k represents an integer of 2 to 8, and m represents 1 or 2. In the metal complex (A), the type of the transition metal is not particularly limited, and a metal of Groups 3 to 11 of the periodic table can be used.
Periodic Table 4 metal (titanium Ti, zirconium Zr, etc.), Periodic Table 5 metal (vanadium V, niobium Nb, etc.), Periodic Table 6 metal (chromium Cr, molybdenum Mo,
Tungsten W, etc.), periodic table group 7 metals (manganese M
n, technetium Tc, rhenium Re, etc.), periodic table 8
Group metal (iron Fe, ruthenium Ru, etc.), group 9 metal (cobalt Co, rhodium Rh, etc.), group 10 metal (nickel Ni, palladium Pd, platinum Pt, etc.), group 11 metal (copper Cu) , Silver Ag, gold Au, etc.). Particularly preferred transition metals are Periodic Table 7 metals (such as Mn), Periodic Table 8 metals (such as Fe and Ru), Periodic Table 9 metals (such as Co and Rh), and Periodic Table 10
Group metals (Ni, Pd, etc.), Periodic Table 11 metals (Cu, etc.), among which Mn, Fe, Co, Ni, C
u, Ru, Rh, Pd and the like are preferable. The valence of the metal is not particularly limited, and is about 2 to 8, preferably about 2 to 6 (for example, about 2 to 4).

In the above formula (1), the organic group represented by X (alkyl, alkenyl, cycloalkyl, aryl, substituted aryl, aralkyl group, etc.) may contain a nitrogen atom or an oxygen atom. Alternatively, the oxygen atom may be directly bonded to A in the formula (1). Further, the organic group X may have various substituents.

As the metal complex (A), a complex represented by the following formula (1A) and / or (2A) is preferably used.

[0022]

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(Wherein Y ^{1 to} Y ³ are the same or different,
R ¹ or R ^2a represents an oxygen atom, a nitrogen atom or a carbon atom;
And R ^2b are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group. R ¹ , R ^2a or R ^2b may be different depending on n, p or q, and may together form an unsaturated or saturated hydrocarbon ring, an aromatic hydrocarbon ring or a heterocyclic ring. n, p and q each independently represent an integer of 1 to 3. k is the same as above. In the above formulas (1A) and (2A), R ¹ , R ^2a and R
^{As the} alkyl group represented by ^2b , methyl, ethyl,
C _1-12 alkyl groups (especially C _1-6 alkyl groups) such as propyl, butyl, t-butyl and the like; cycloalkyl groups such as C.sub.1 such as cyclopentyl and cyclohexyl
_4-8 cycloalkyl groups and the like; alkenyl groups include C _2-10 alkenyl groups such as allyl and vinyl groups; and aryl groups include C _6-12 alkenyl groups such as phenyl, tolyl and naphthyl groups.
Aryl group and the like; Examples of the aralkyl group include a C _7-14 aralkyl group such as a benzyl group and a phenethyl group.

A plurality of R ¹ , R ^2a , or R ^2b may be present depending on Y ^{1 to} Y ³ (depending on n, p or q). In the formula (1A), R ¹ is adjacent to each other. Y ¹ to
And may form a ring together. The ring includes a saturated hydrocarbon ring (such as a saturated C _4-8 hydrocarbon ring such as a cyclobutane, cyclopentane, and cyclohexane ring) and an unsaturated hydrocarbon ring (such as an unsaturated carbon ring such as a cyclopentene and cyclohexene ring).
_5-8 hydrocarbon rings), aromatic hydrocarbon rings (benzene,
A heterocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur (such as an aromatic C _6-12 hydrocarbon ring such as naphthalene); and nitrogen as a heteroatom such as a pyrrole, pyrrolidine, piperidine, piperazine and piperidine ring. A 5- to 8-membered heterocycle containing an atom, a 5- to 8-membered heterocycle containing an oxygen atom as a hetero atom such as furan, and the like.

Preferred examples of the metal complex (A) include complexes represented by the following formulas (ia) to (ic) and (iia).

[0026]

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Where R^1a~ R^1f, And R^2aAnd R^2b
Are the same or different and are a hydrogen atom, C _1-6Alkyl group,
C_4-8Cycloalkyl group, C_6-12Aryl group, and C
_7-14Indicates at least one selected from aralkyl groups
Then R^1bAnd R^1cAre saturated or unsaturated hydrocarbons together
May form an elementary ring, a heterocyclic ring, an aromatic hydrocarbon ring, or the like.
K, R^1d~ R^1fAt least two of them get bored together
Sum or unsaturated hydrocarbon ring, heterocyclic ring, aromatic hydrocarbon ring
It may be formed. M and k are the same as above. The formulas (1), (1A) and (2A), and (ia) to (i)
In c) and (iia), the ligand di-coordinating to metal M
Thio compounds can be used alone or in combination of two or more
You. Particularly preferred dithio compounds are of the formula (ib)
Dithiocarbamate or dithiopho represented by (iia)
It is a spate.

As the dithiocarbamate, for example, N
N-alkyldithiocarbamates such as -methyl-dithiocarbamate and N-ethyldithiocarbamate (especially N- _{C1-10alkyldithiocarbamate and the} like);
N, N-dimethyldithiocarbamate, N, N-diethyldithiocarbamate, N, N-di-n-propyldithiocarbamate, N, N-di-i-propyldithiocarbamate, N, N-di-n-butyldithio Carbamate, N, N-di-i-butyldithiocarbamate, N,
N-di-s-butyldithiocarbamate, N, N-di-
N, N-dialkyldithiocarbamates such as n-amyldithiocarbamate, N, N-di-i-amyldithiocarbamate, N, N-di-n-hexyldithiocarbamate, N-methyl-Ni-propyldithiocarbamate (Especially N, N-diC _1-12 alkyldithiocarbamate) and the like; N-phenyldithiocarbamate and the like
-Aryl carbamates (such as N-C _6-12 aryl carbamates); N-methyl-N-phenyldithiocarbamate, N-ethyl-N-phenyldithiocarbamate, Nn-propyl-N-phenyldithiocarbamate, N- N-alkyl-N-aryldithiocarbamates such as n-butyl-N-phenyldithiocarbamate and Ni-amyl-N-phenyldithiocarbamate (especially N-C _1-10 alkyl-N-C _6-12 aryldithio N-cycloalkyldithiocarbamates such as N-cyclohexyl carbamate
-C _4-8 such cycloalkyl dithiocarbamate) such as; N, N-dicyclopentyl dithiocarbamate,
N, N- N, such as dicyclohexyl dithiocarbamate, N- dicycloalkyl dithiocarbamates (particularly N, N- di C _4-8 such cycloalkyl dithiocarbamate) such as; N- allyl dithiocarbamate such as N- alkenyl dithiocarbamate ( N-C _2-10 alkenyl dithiocarbamate) such as; N, N- N, such as diallyl dithiocarbamate, N- dialkenyl dithiocarbamate (particularly N, N- di C _2-8 alkenyl dithiocarbamate, etc.); N- benzyl such as N- aralkyl dithiocarbamate such as dithiocarbamate (particularly N-C _{7- 10} aralkyl dithiocarbamate); N, such as N- dibenzyl dithiocarbamate N, N- di aralkyl dithiocarbamate (particularly N, N- di-C _7-14 and aralkyl dithiocarbamate) Etc.; N- methyl -N- benzyl dithiocarbamate, N- ethyl -N- N-alkyl -N- aralkyl dithiocarbamates such as benzyl carbamate (especially N-C _1-8 alkyl -N-C _7-10 aralkyl dithiocarbamate And the like; and heterocyclic dithiocarbamates such as pyrrolidyldithiocarbamate, piperidyldithiocarbamate, and morpholinyldithiocarbamate.

As the dithiophosphate, O-methyl
Dithiophosphate, O-ethyldithiophosphate
Any O-alkyldithiophosphate (particularly OC_1-12
Alkyldithiophosphate, etc.); O, O'-di
Methyldithiophosphate, O, O'-diethyldithio
Phosphate, O, O'-di-n-propyldithiophospho
Fate, O, O'-di-i-propyldithiophosphate
, O, O'-di-n-butyldithiophosphate,
O, O'-di-i-butyldithiophosphate, O,
O'-di-n-hexyldithiophosphate, O, O '
O, O'- such as -di-n-decyldithiophosphate
Di C_1-16Alkyl dithiophosphate (particularly O, O'-
Di C_1-12Alkyldithiophosphate, etc.); O-
O-cycloalkyl such as cyclohexyldithiophosphate
Lucildithiophosphate (OC _5-8Cycloalkyl
Dithiophosphate, etc.); O, O'-dicyclo
O, O'-dicycloa, such as xyldithiophosphate
Rukyldithiophosphate (particularly O, O'-diC_5-8Shi
O-phenyldithio)
O-aryldithiophosphates such as ophosphate
(Especially OC_6-12Aryl dithiophosphate)
O, O'-diphenyldithiophosphate, O,
O, such as O'-di-o-tolyldithiophosphate,
O'-diaryldithiophosphate (O, O'-diC
_6-12Aryldithiophosphate) and the like.

Such ligands having a dithio unit can be used alone or in combination of two or more.

Preferred ligands are dithiocarbamates, especially N, N-dimethyldithiocarbamate,
N, such as N- diethyldithiocarbamate N, N- di C _1-6 alkyl dithiocarbamate, N, such as N- dibenzyl dithiocarbamate N, N- di C _7-10 aralkyl dithiocarbamates, such as piperidyl dithiocarbamate And heterocyclic dithiocarbamates (5- to 6-membered heterocyclic dithiocarbamates containing a nitrogen atom as a hetero atom).

In the above formula, the coordination number k corresponds to the valence (oxidation number) of the central metal M of the metal complex, and is an integer of 2 to 8, preferably 2 to 6 (for example, 2 to 4). Is an integer of degree.

The above-mentioned metal complexes can be used alone or in combination of two or more.

The kind of the radical initiator (B) constituting the polymerization initiator system of the present invention is not particularly limited, and a conventional radical initiator (radical generator), for example, an azo compound, an organic peroxide, an inorganic A peroxide or the like can be used.

As the azo compound, azobisnitrile [for example, 2,2'-azobisisobutyronitrile (A
2,2′-azobisbutyronitriles such as IBN) and 2,2′-azobis (2-methylbutyronitrile);
2,2′-azobisvaleronitriles such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile); 2,2'-azobispropionitrile such as 2'-azobis (2-hydroxymethylpropionitrile); 1,1'-azobiscyclohexane-1
1,1′-azobis-1-alkanenitrile such as carbonitrile, especially 1,1′-azobis-1-cycloalkanenitrile (for example, 1,1′-azobis-1)
-C _5-8 cycloalkane carbonitrile), 4,4'-azobis (4-cyanovaleric acid) and azo bis cyano carboxylic acids, such as, azonitrile [2- (carbamoylazo) Azobuchiro such isobutyronitrile Nitriles; azovaleronitriles such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, etc.], azobisalkanes [eg, 2,2′-azobis (2-methylpropane), 2,2 ′ - azobis (2,4,4-trimethylpentane), such as 2,2'-azobis C _3-10 alkanes, etc.], dimethyl 2,2'-azobis isobutyrate and the like.

Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, decanoyl peroxide and lauroyl peroxide;
Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, and 1,1-bis (t-butylperoxy) -3,3
5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4
Peroxyketals such as 4-di-t-butylperoxycyclohexyl) propane; hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide; di-t-butyl peroxide; dicumyl peroxide; t Dialkyl peroxides such as -butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, and peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate , T-butyl peroxybenzoate, 2,
And peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane.

Examples of the inorganic peroxide include hydrogen peroxide, persulfate (potassium persulfate, ammonium persulfate, etc.).

As the redox polymerization initiator, a combination of a persulfate or a peroxide and a reducing agent, for example,
Hydrogen peroxide-ferrous salt, benzoyl peroxide-
Examples include dimethylaniline-based or cerium (IV) salt-alcohol-based combinations.

The radical initiator is preferably a non-halogen radical initiator from the viewpoint of preventing the polymer from containing halogen. As the radical initiator, an azo compound (such as AIBN) and peroxides are usually used. In particular, azo compounds are preferred.

These radical initiators can be used alone or in combination of two or more.

For generating radicals from the radical initiator, for example, heat, light, radiation, an oxidation-reduction reaction and the like can be employed. These radical generating means may be applied alone or in combination of two or more.

The ratio of the metal complex to the radical initiator is as follows: metal complex (A) / radical initiator (B) = 0.1 / 1 to 1
It can be selected from a wide range of about 0/1 (molar ratio).
0.25 / 1 to 4/1 (molar ratio), preferably 0.25
/ 1 to 3.5 / 1 (for example, 0.25 / 1 to 3/1) (molar ratio), especially about 0.25 / 1 to 2/1 (molar ratio). When the molar ratio is smaller than 0.1, the molecular weight distribution is widened, and when the molar ratio is larger than 10, the polymerization rate may be reduced.

In the present invention, when at least one vinyl monomer is polymerized in the presence of a polymerization initiator system containing a transition metal compound and a radical initiator as described above, the molecular weight distribution is narrow and the molecular weight is small. A controlled polymer can be obtained.

The vinyl monomer is not particularly limited as long as it can be polymerized by the polymerization initiator system, and various polymerizable vinyl monomers such as an aromatic vinyl monomer and a heterocyclic vinyl monomer can be used. Monomers (such as N-vinylpyrrolidone),
α, β-unsaturated carboxylic acids or derivatives thereof, α, β-unsaturated nitriles, carboxylic acid vinyl esters, conjugated diene monomers, olefin monomers, vinyl halides, vinylidene halides and the like can be used.

As the aromatic vinyl monomer, styrene,
Alkylstyrenes (e.g., vinyltoluenes such as o-, m- and p-methylstyrene, vinylxylenes such as 2,4-dimethylstyrene, p-ethylstyrene,
p-isopropylstyrene, p-butylstyrene, p-
t-butylstyrene, etc.), α-alkylstyrene (eg, α-methylstyrene, α-methyl-p-methylstyrene, etc.), alkoxystyrene (eg, o-, m
-And p-methoxystyrene, pt-butoxystyrene, etc.), halostyrene (for example, o-, m- and p-).
Chlorostyrene, p-bromostyrene, etc.), styrenesulfonic acid or an alkali metal salt thereof, and the like.
Preferred styrene-based monomers include styrene, vinyltoluene and the like, and styrene is particularly preferred.

The α, β-unsaturated carboxylic acids and derivatives thereof include, for example, α, β-unsaturated carboxylic acids, α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid amides, β-unsaturated carboxylic imides and the like are included.

Examples of the α, β-unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid, polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and acid anhydrides thereof (for example, And maleic anhydride.

As the α, β-unsaturated carboxylic acid ester, the above-mentioned alkyl esters of α, β-unsaturated carboxylic acids (particularly, C _1-20 alkyl esters) and the like can be used. (Meth) methyl acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
C _1-14 alkyl (meth) acrylates such as octyl (meth) acrylate and lauryl (meth) acrylate, and (meth) such as cyclohexyl (meth) acrylate
Acrylic acid _C4-10 cycloalkyl esters, or mono or dialkyl maleate, mono or dialkyl fumarate, mono or dialkyl itaconate, and the like corresponding to these (meth) acrylic esters are exemplified. Further, the alkyl esters may have a substituent such as a hydroxyl group, a glycidyl group, an amino group or an N-alkylamino group. As the substituent-containing ester, hydroxyalkyl (meth) acrylate (hydroxyethyl ( (Meth) acrylate, hydroxy C _2-10 alkyl (meth) acrylate such as hydroxypropyl (meth) acrylate, etc.), glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl ( (Meth) acrylate and the like.

Examples of the α, β-unsaturated carboxylic acid amide include (meth) acrylamide and derivatives thereof (for example, N, N-methyl (meth) acrylamide and the like;
-Dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc.), and fumaric acid amides corresponding thereto (such as fumaric acid, fumaric acid or derivatives thereof).

As the α, β-unsaturated carboxylic imide, for example, maleimide or a derivative thereof (for example, N-
Methylmaleimide, N-phenylmaleimide, etc.).

The α, β-unsaturated nitrile includes vinyl cyanide compounds such as (meth) acrylonitrile.

The vinyl carboxylate includes vinyl C _1-10 carboxylates such as vinyl formate, vinyl acetate, vinyl propionate and vinyl pivalate (especially C _1-10).
1-6 carboxylic acid vinyl ester).

As the conjugated diene monomer, butadiene, isoprene, chloroprene, neoprene, 1,3-
Pentadiene, 2,3-dimethyl-1,3-butadiene, piperiene, 3-butyl-1,3-octadiene,
Examples thereof include C _4-16 dienes such as phenyl-1,3-butadiene (preferably C _4-10 dienes).

As the olefin-based monomer, ethylene,
Examples thereof include C _2-10 alkenes (preferably C _2-6 alkenes) such as propylene and butene (such as isobutene).

Examples of the vinyl halide include vinyl fluoride, vinyl chloride, and vinyl bromide. Examples of the vinylidene halide include vinylidene fluoride, vinylidene chloride, and vinylidene bromide.

In order to avoid introduction of halogen into the polymer, it is preferable to use a non-halogen monomer. Preferred vinyl monomers are styrene monomers and (meth) acrylic monomers ((meth) acrylic acid, (meth) acrylic acid esters (especially methyl methacrylate, acrylic acid C).
_2-10 alkyl esters), (meth) acrylonitrile, etc.).

The vinyl monomers can be used alone or in combination of two or more. When two or more kinds are used in combination, for example, a random copolymer is obtained by adding and using a plurality of monomers at the same time, and a method of sequentially adding the monomers, for example, a method of adding the first monomer After the polymerization is completed, the second monomer is added to complete the polymerization, and then the third monomer is added, so that the block copolymer is obtained by successively adding the monomers. By changing the composition ratio of a plurality of monomers over time, a gradient copolymer can be obtained.

The molecular weight of the polymer can be determined by the ratio between the vinyl monomer and the radical initiator. Therefore, by changing the ratio between the vinyl monomer and the radical initiator, the molecular weight can be controlled, and a polymer having a desired molecular weight can be obtained.

The ratio between the vinyl monomer and the polymerization initiator is, for example, the ratio of the vinyl monomer / radical initiator (B)
= 5/1 to 10,000 / 1 (molar ratio), usually about 5/1 to 5000/1 (molar ratio).

The molecular weight of the polymer is determined by the number average molecular weight (Mn).
Is 1,000 to 500,000, preferably 1,500
１００100,000 and the molecular weight distribution (Mw / M
n) is 1.05-2, preferably 1.05-1.9.
(For example, about 1.05 to 1.7).

The polymerization method of the vinyl monomer is not particularly limited, and a conventional polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or bulk-suspension polymerization can be employed.

In the case of performing the solution polymerization, the solvent is not particularly limited, and a conventional solvent such as an aromatic hydrocarbon (benzene, toluene, ethylbenzene, xylene, etc.), an alicyclic hydrocarbon (cyclohexane, etc.), Aliphatic hydrocarbons (hexane, octane, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.),
Ethers (dioxane (such as 1,4-dioxane),
Tetrahydrofuran and the like, esters (eg, ethyl acetate), amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide) and the like can be used. Particularly, toluene, ethylbenzene, benzene, N, N-dimethylformamide and the like are preferable.
Such solvents can be used alone or in combination of two or more.

The polymerization can be carried out under normal pressure or under pressure, depending on the type of the vinyl monomer.

The polymerization temperature is, for example, from 0 to 200 ° C., depending on the type of polymerization method, constitution of the polymerization initiator system, polymerization rate and the like.
Can be selected from a wide range of degrees, usually 50-200 ° C,
Preferably 60 to 160 ° C (for example, 80 to 140 ° C)
You can choose from a range of degrees.

The polymerization may be carried out usually in an atmosphere of an inert gas such as nitrogen or argon, for example, under a flow of an inert gas.

The polymer may be separated and purified, for example, after the polymerization reaction, if necessary, by diluting with a solvent and precipitating in a poor solvent, or by removing volatile components such as monomers and solvents. Good.

The polymerization initiator system of the present invention can be applied to various vinyl monomers and, as described above, can produce a polymer having a narrow molecular weight distribution and a controlled molecular weight. The obtained polymer can be used in various applications (eg, resin for molding such as film molding and injection molding, resin for coating such as paint, compatibilizer, etc.) depending on the type of vinyl monomer, structure of the polymer, and the like. , Thermoplastic elastomers, etc.).

[0068]

According to the present invention, when a polymerization initiator system containing a specific metal complex and a radical initiator and containing no halogen element is used, various vinyl monomers can be radically polymerized in a living manner. . Therefore, the primary structure such as the molecular weight and the molecular weight distribution of the polymer can be controlled, and a polymer having a narrow molecular weight distribution can be obtained.

[0069]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

The operations in the following Examples and Comparative Examples were performed in a dry nitrogen atmosphere unless otherwise specified.
Reagents were collected from the container with a syringe and added to the reaction system. The monomer and the solvent were purified by distillation in the presence of a desiccant and deoxygenated by blowing dry nitrogen before use.

The polymerization rates and the molecular weights of the polymers obtained in Examples and Comparative Examples were measured by the following methods. (Polymerization ratio) The monomer remaining in the reaction solution obtained by the polymerization reaction was subjected to an internal standard method (internal standard reagent: tetrahydronaphthalene) using gas chromatography (GC, manufactured by Shimadzu Corporation, column: PEG6000). Quantified by
The amount of reduction of the monomer was calculated as a conversion rate into a polymer (polymerization rate). (Molecular weight) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC, manufactured by JASCO Corporation) under the following conditions.

Column: Shodex K-805L, 3 in series Solvent: chloroform Column temperature: 40 ° C. Detector: Differential refractometer (RI) Flow rate: 1 mL / min Example 1 Tris (N, N-diethyldithiocarbamate) iron 7
0.1 mg (0.14 mmol, 20 mmol / L) was precisely weighed in a Schlenk reaction tube under an argon atmosphere, and 1.6 mL (14 mmol, 2.0 mol /
L), tetrahydronaphthalene 0.33 mL, toluene 4.44 mL, AIBN toluene solution (concentration 0.25 m
ol / L) 0.56 mL (0.14 mmol, 20 mm
ol / L) and stirred well. 1m of mixed solution
After sealing in a test tube for each L, the polymerization was started by heating to 120 ° C.

When the reaction time was 9 hours and 48 hours, the polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. The polymerization rate is 30% after 9 hours, 4
It was 70% after 8 hours.

After diluting the polymerization solution with toluene, metal complex components and the like were removed with an adsorbent, and the monomers and solvents were evaporated to obtain a polymer. The molecular weight and molecular weight distribution of the obtained polystyrene were such that Mn = 26 after 9 hours.
00, Mw / Mn = 1.23, after 48 hours, Mn =
5100, Mw / Mn = 1.17. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 140 ° C. and the reaction time was 4 hours and 30 hours. After 4 hours, the conversion is 40%, Mn = 3000, Mw / Mn =
1.22, and after 30 hours, the conversion was 80%.
n = 6000 and Mw / Mn = 1.26. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 3 Tris (N, N-diethyldithiocarbamate) iron
The same procedure as in Example 1 was performed except that 0.5 mg (0.07 mmol, 10 mmol / L) was used, and the reaction time was changed to 8 hours and 50 hours. After 8 hours, the conversion is 40%,
Mn = 3400, Mw / Mn = 1.57, and after 50 hours, the polymerization rate was 68%, Mn = 5800, Mw / M.
n = 1.49. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 4 Tris (N, N-diethyldithiocarbamate) iron
05.1 mg (0.21 mmol, 30 mmol / L)
It carried out similarly to Example 1 except having used and making reaction time 24 hours and 100 hours. After 24 hours, the polymerization rate is 30%, Mn = 2000, Mw / Mn = 1.17. After 100 hours, the polymerization rate is 59%, Mn = 340.
0, Mw / Mn = 1.17. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 5 Tris (N, N-diethyldithiocarbamate) iron 7
0.1 mg (0.14 mmol, 20 mmol / L) was precisely weighed into a Schlenk reaction tube under an argon atmosphere, and styrene (4.81 mL, 42 mmol, 6.0 mol / L) was added thereto.
L), tetrahydronaphthalene 1 mL, toluene 0.5
6 mL, AIBN toluene solution (concentration: 0.25 mol /
L) 0.56 mL (0.14 mmol, 20 mmol /
L) was added and stirred well. Each 1 mL of the mixed solution was sealed in a test tube, and then heated to 120 ° C. to start polymerization.

At the time when the reaction time was 8 hours and 100 hours, the polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. The result of the polymerization was evaluated in the same manner as in Example 1. After 8 hours, the conversion is 44% and Mn = 930.
0, Mw / Mn = 1.38, and after 100 hours,
The polymerization rate is 89%, Mn = 20,500, Mw / Mn =
1.31. All of the obtained polystyrene,
The GPC curve was unimodal.

Example 6 Tris (N, N-diethyldithiocarbamate) iron
5.0 mg (0.07 mmol, 10 mmol / L),
0.25 mol / L AIBN toluene solution 0.28 m
L (0.07 mmol, 10 mmol / L)
The procedure was performed in the same manner as in Example 5 except that the reaction time was set to 24 hours and 100 hours. After 24 hours, the polymerization rate is 54%,
Mn = 21600, Mw / Mn = 1.31, and 10
After 0 hour, the polymerization rate is 85%, Mn = 31200, M
w / Mn = 1.30. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 7 Tris (N, N-diethyldithiocarbamate) copper 5
0.4 mg (0.14 mmol, 20 mmol / L) was precisely weighed in a Schlenk reaction tube under an argon atmosphere, and 1.6 mL of styrene (14 mmol, 2.0 mol / L) was added thereto.
L), tetrahydronaphthalene 0.33 mL, toluene 4.46 mL, AIBN toluene solution (concentration 0.25 m
ol / L) 0.56 mL (0.14 mmol, 20 mm
ol / L) and stirred well. 1m of mixed solution
After sealing in a test tube for each L, the polymerization was started by heating to 120 ° C.

When the reaction time was 3 hours and 30 hours, the polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. The result of the polymerization was evaluated in the same manner as in Example 1. After 3 hours, the conversion was 34% and Mn = 470.
0, Mw / Mn = 1.87, and after 30 hours, the conversion was 79%, Mn = 7900, Mw / Mn = 1.60.
Met. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 8 Polymerization was carried out in the same manner as in Example 4 except that the polymerization temperature was 140 ° C., and the reaction times were 3.5 and 30 hours. After 3.5 hours, the conversion was 28%, Mn = 3300, Mw / Mn.
= 1.58, and after 30 hours, the polymerization rate is 89%,
Mn = 6600 and Mw / Mn = 1.56. Each of the obtained polystyrenes had a monomodal GPC curve.

Example 9 Tris (N, N-dibenzyldithiocarbamate) iron 1
22.2 mg (0.14 mmol, 20 mmol / L)
Was precisely weighed into a Schlenk reaction tube under an argon atmosphere, and styrene 1.60 mL (14 mmol, 2.0 mol
/ L), octane 0.27 mL, toluene 4.45 m
L, AIBN toluene solution (concentration: 0.25 mol / L)
0.56 mL (0.14 mmol, 20 mmol / L)
Was added and stirred well. Each 1 mL of the mixed solution was sealed in a test tube, and then heated to 120 ° C. to start polymerization.

When the reaction time passed 24 hours and 252 hours, the polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. When the polymerization rate of styrene was measured, the polymerization rate after 24 hours was 44% and 252.
After the elapse of time, the polymerization rate was 72%.

After diluting the polymerization solution with toluene, metal complex components and the like were removed with an adsorbent, and volatile components such as monomers and solvents were evaporated to obtain a polymer. When the molecular weight of the obtained polystyrene was measured, Mn of the polystyrene after 24 hours passed was 3400, and Mw / Mn was 1.1.
4, the Mn of the polystyrene after 252 hours passed was 520
0, Mw / Mn was 1.23, and these GPC curves were monomodal.

Example 10 A polymerization reaction was carried out in the same manner as in Example 9 except that the polymerization temperature was set to 100 ° C., and the termination time of the polymerization was set to 100 hours and 407 hours, and the results were analyzed.
After 100 hours, the polymerization rate is 49%, Mn is 3300,
Mw / Mn was 1.11, the polymerization rate after 407 hours passed was 71%, Mn was 5000, Mw / Mn was 1.12, and these GPC curves were monomodal.

Example 11 In Example 9, styrene (4.81 mL, 42 mmo) was used.
1, 6.0 mol / L), the polymerization reaction was carried out in the same manner as in Example 9 except that the octane was 0.80 mL, the toluene was 0.71 mL, and the polymerization termination time was 8 hours and 69 hours, and the results were analyzed. did. After 8 hours, the polymerization rate is 38.
%, Mn is 9,300, Mw / Mn is 1.18, the polymerization rate after 69 hours is 76%, Mn is 17,400, Mw /
Mn was 1.23 and these GPC curves were unimodal.

Example 12 Tris (N, N-diethyldithiocarbamate) iron 7
0.1 mg (0.14 mmol, 20 mmol / L) was precisely weighed in a Schlenk reaction tube under an argon atmosphere, and 1.50 mL of methyl methacrylate (14 mmol, 2.
0 mol / L), octane 0.25 mL, N, N-dimethylformamide 4.62 mL, AIBN solution of N, N-dimethylformamide (concentration 0.25 mol / L)
0.56 mL (0.14 mmol, 20 mmol / L)
Was added and stirred well. After 1 mL of the mixed solution was sealed in a test tube, the mixture was heated to 80 ° C. to start polymerization.

At the time when the reaction time passed 4 hours and 30 hours, the polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. When the polymerization rate of methyl methacrylate was measured, the polymerization rate after 4 hours was 57%,
After a lapse of 30 hours, the polymerization rate was 94%.

After diluting the polymerization solution with toluene, the metal complex component and the like were removed by an adsorbent, and volatile components such as monomers and solvents were evaporated to obtain a polymer. When the molecular weight of the obtained polymethyl methacrylate was measured, the Mn of the polymethyl methacrylate after 4 hours was 4200,
Mw / Mn was 1.77, Mn of polymethyl methacrylate after 30 hours was 7,200, and Mw / Mn was 1.46.
And these GPC curves were unimodal.

Comparative Example 1 The procedure of Example 1 was repeated except that tris (N, N-diethyldithiocarbamate) iron was not added, the amount of toluene added was 4.51 mL, and the reaction time was 30 hours. After 30 hours, the conversion is 74%, Mn = 1300, Mw /
Mn = 4.09. The obtained polystyrene had a bimodal GPC curve.

Comparative Example 2 The amount of toluene added was 5.02 m without the addition of AIBN.
L, and the same procedure as in Example 7 except that the reaction time was changed to 50 hours. No polymer was obtained after 50 hours.

As is clear from the examples and comparative examples, in the examples, as the polymerization rate increases, the number average molecular weight of the polymer increases, and it can be seen that the polymerization proceeds in a living manner. Also, with the increase of the polymerization rate, the molecular weight distribution,
It is significantly narrower than that of Comparative Example 1. Further, in Comparative Example 1 in which the metal complex was not added, the molecular weight distribution curve showed bimodality, whereas in Examples, each case showed a monomodal peak. Comparative Example 2 without adding a radical initiator
In this case, the polymerization reaction did not proceed, and it was found that the presence of a radical initiator was essential.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08F 20/00 C08F 20/00 (72) Inventor Yoshio Okamoto 2-66 Yadacho, Higashi-ku, Nagoya-shi, Aichi Prefecture Naoya Ota-tamachi 222 (72) Inventor Yoshimichi Okano 1239 Shinzai, Aboshi-ku, Himeji-shi, Hyogo Prefecture Inside Dai-ichi Kagaku Kogyo Co., Ltd. (72) Inventor Kazutoshi Terada 2045-1, Sakurazu, Kurashiki-shi, Okayama Pref. Daiji Ida 2045-1 Sazu, Kurashiki-shi, Okayama Pref. Kura Rekurashi Research Institute Co., Ltd. (72) Inventor Yoshiaki Kano 1-8 Kasumi, Yokkaichi-shi, Mie Tosoh Co., Ltd. Yokkaichi Research Laboratories 1-8 Ichika Ichi, Tosoh Corporation Yokkaichi Research Laboratories (72) Inventor Chitsubaki Kitahata 23 Uji Kozakura, Uji-shi, Kyoto Unitika Ltd.Central Research Laboratories (72) Inventor Kazunobu Yamada 23 Uji Kozakura, Uji-shi, Kyoto Unitika Central Research Institute Co., Ltd. In-plant F-term (reference) 4J011 AA07 AC03 HA03 HB22 JB22 KB22 4J015 DA13 DA23 DA24 DA25 DA34 DA35 4J100 AA01P AA02P AA03P AA06P AA15P AB02P AB03P AB04 AL07P AB08P AB09P AC03P AC04P02A03P AL34P AL36P AL39P AL41P AL44P AL46P AM02P AM15P AM17P AM19P AM21P AM33P AM37P AM45P AM48P AS01P AS02P AS03P AS04P AS06P AS07P BA03P BA04P BA05P BA31P BA56P BC02P BC04P BC43P CA01 CA03 DA01 DA03 FA03

Claims (12)

[Claims] 1. A polymerization initiator system for living polymerization, which comprises the following formula (1): (Where A represents a carbon or phosphorus atom, M represents a transition metal element, X represents an organic group optionally containing an oxygen atom or a nitrogen atom, k is an integer of 2 to 8, m is 1 Or 2)) and a radical initiator (B). 2. The polymerization initiator system according to claim 1, wherein the metal complex (A) is a complex of a transition metal belonging to Groups 7 to 11 of the periodic table. 3. The polymerization initiator system according to claim 1, wherein the metal complex (A) is a complex of at least one metal selected from manganese, iron, cobalt, nickel, copper, ruthenium, rhodium and palladium. 4. A polymerization initiator for living polymerization, which comprises the following formulas (ia) to (ic) or (iia): (Wherein, R ^{1a to} R ^1f and R ^2a and R ^2b are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group, and R ^1b and R ^1c are Wherein M and k are the same as defined above) and a radical initiator (B). . 5. R ^{1a to} R ^1f, R ^2a and R ^2b are the same or different and each is a C _1-6 alkyl group, a C _4-8 cycloalkyl group, a C _6-12 aryl group, and a C _7-14 The polymerization initiator system according to claim 4, which is at least one selected from aralkyl groups. 6. The polymerization initiator system according to claim 1, wherein the metal complex (A) is a dithiocarbamate complex. 7. The radical initiator (B) is an azo compound,
5. The polymerization initiator system according to claim 1, wherein the polymerization initiator is at least one selected from organic peroxides and inorganic peroxides. 8. A metal complex (A) and a radical initiator (B)
The polymerization initiator system according to claim 1 or 4, wherein the ratio of the former is the former / the latter = 0.1 / 1 to 10/1 (molar ratio). 9. A polymer obtained by polymerizing at least one vinyl monomer in the presence of the polymerization initiator system according to claim 1 or 4. 10. The polymer according to claim 9, wherein the vinyl monomer is at least one selected from a styrene monomer and a (meth) acrylic monomer. 11. A number average molecular weight (Mn) of 1000 to 5
00,000 and a molecular weight distribution (Mw / Mn) of 1.
10. The polymer according to claim 9, wherein the number is from 0.5 to 1.9. 12. A method for producing a polymer, comprising polymerizing a vinyl monomer in the presence of the polymerization initiator system according to claim 1.